Abstract
In this work, the thermodynamic properties of 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide/primary alcohol (methanol to 1-nonanol) mixtures were studied. The densities, viscosities, and electrical conductivities of the mixtures were determined for a range of compositions up to the solubility limit of the alcohol in the ionic liquid at room temperature. From these data, excess molar volumes and viscosity deviations were calculated. The changes in the structure of the ionic liquid upon addition of the primary alcohols are discussed. We also considered the relationship between the macroscopic properties observed in the present study and the Raman spectral changes reported in our previous study. We explained the behavior of the systems at the molecular level, especially at lower alcohol concentrations, by a concept where the alcohols occupy spaces formed inside the nanoheterogeneous structure of the ionic liquid.
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Wang, Y., Voth, G.A.: Unique spatial heterogeneity in ionic liquids. J. Am. Chem. Soc. 127, 12192–12193 (2005)
Lopez, J.N.A.C., Pádua, A.A.H.: Nanostructural organization in ionic liquids. J. Phys. Chem. B 110, 3330–3335 (2006)
Triolo, A., Russina, O., Bleif, H.-J., Di Cola, E.: Nanoscale segregation in room temperature ionic liquids. J. Phys. Chem. B 111, 4641–4644 (2007)
Ozawa, R., Hayashi, S., Saha, S., Kobayashi, A., Hamaguchi, H.: Rotational isomerism and structure of the 1-butyl-3-methylimidazolium cation in the ionic liquid state. Chem. Lett. 32, 948–949 (2003)
Nishikawa, K., Wang, S., Tozaki, K.: Rhythmic melting and crystallizing of ionic liquid 1-butyl-3-methylimidazolium bromide. Chem. Phys. Lett. 458, 88–91 (2008)
Zheng, Y.-Z., Zhoud, Y., Denge, G., Guo, R., Chen, D.-F.: Insight into the structure and interaction properties of 1-propylnitrile-3-methylimidazolium bis(trifluoromethylsulfonyl)amide and chloroform mixtures. J. Mol. Liq. 283, 748–755 (2019)
Blokhin, A.V., Paulechka, Y.U., Strechan, A.A., Kabo, G.J.: Physicochemical properties, structure, and conformations of 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl) amide [C4mim]NTf2 ionic liquid. J. Phys. Chem. B 112, 4357–4364 (2008)
Xie, L.L., Favre-Reguillon, A., Wang, X.X., Fu, X.Z., Pellet-Rostaing, S., Toussaint, G., Geantet, C., Vrinatd, M., Lemaire, M.: Selective extraction of neutral nitrogen compounds found in diesel feed by 1-butyl-3-methyl-imidazolium chloride. Green Chem. 10, 524–531 (2008)
Huddleston, J.G., Visser, A.E., Reichert, W.M., Willauer, H.D., Broker, G.A., Rogers, R.D.: Characterization and comparison of hydrophilic and hydrophobic room temperature ionic liquids incorporating the imidazolium cation. Green Chem. 3, 156–164 (2001)
Bonhote, P., Dias, A., Papageorgiou, N., Kalyanasundaram, K., Gratzel, M.: Hydrophobic, highly conductive ambient-temperature molten salts. Inorg. Chem. 35, 1168–1178 (1996)
Koch, V.R., Nanjundah, C., Appetecchi, G.B., Scrosati, B.: The interfacial stability of Li with two new solvent-free ionic liquids: 1,2-dimethyl-3-propylimidazolium amide and methide. J. Electrochem. Soc. 142, L116–L118 (1995)
Yoshimura, Y., Hattori, S., Mori, T., Kaneko, K., Ueda, J., Takekiyo, T., Masuda, Y., Shimizu, A.: An insight into the filling of the nanoheterogeneous structures of 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide by primary alcohols. J. Mol. Liq. 300, 112351 (2020)
Noack, K., Leipertz, A., Kiefer, J.: Molecular interactions and macroscopic effects in binary mixtures of an imidazolium ionic liquid with water, methanol, and ethanol. J. Mol. Struct. 1018, 45–53 (2012)
Shrivastav, G., Gupta, A., Rastogi, A., Dhabal, D., Kashyap, H.K.: Molecular dynamics study of nanoscale organization and hydrogen bonding in binary mixtures of butylammonium nitrate ionic liquid and primary alcohols. J. Chem. Phys. 146, 064503 (2017)
Sandhya, M.S., Govinda, V., Bahadur, I., Venkateswarlu, P.: Nature of the molecular interaction between 1-ethyl-3-methylimidazolium methylsulfate ionic liquid with higher chain alcohol through binary mixtures containing thermophysical properties. J. Mol. Liq. 240, 613–621 (2017)
Alavianmehr, M.M., Afshar, S., Aparicio, S., Haghani, A.H., Hosseini, S.M., Khalifeh, R.: Experimental and theoretical study of 2-hydroxyethylammonium formate ionic liquid + alcohol mixtures. J. Mol. Liq. 281, 269–279 (2019)
Agrawal, S., Kashyap, H.K.: Structures of binary mixtures of ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide with primary alcohols: the role of hydrogen-bonding. J. Mol. Liq. 261, 337–349 (2018)
Blanco-Díaz, E.G., Castrejón-Gonzáleza, E.O., López-Cortés, I.Y., Ramos-Estrada, M., Iglesias-Silva, G.A.: Thermodynamic and transport properties of 1-allyl-3-methylimidazolium bis(trifluromethylsulfonyl)imide + 1-propanol liquid mixtures: a molecular dynamics study. J. Mol. Liq. 279, 662–668 (2019)
Gutiérrez, A., Atilhan, M., Alcalde, R., Trenzadod, J.L., Aparicio, S.: Insights on the mixtures of imidazolium based ionic liquids with molecular solvents. J. Mol. Liq. 255, 199–207 (2018)
Trenzado, J.L., Alcalde, R., Atilhanc, M., Aparicio, S.: Molecular dynamics and experimental characterization of [BMIM][BF4] and [BMIM][PF6] with ether cosolvent binary mixtures. J. Mol. Liq. 271, 65–73 (2018)
Alcalde, R., Atilhan, M., Aparicio, S.: Insights on 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide + ethanol liquid mixtures: a molecular dynamics approach. J. Chem. Eng. Data 61, 2729–2737 (2016)
Alcalde, R., Atilhanb, M., Aparicio, S.: Intermolecular forces in 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide + ethanol mixtures. J. Mol. Liq. 258, 1–9 (2018)
Deng, Y., Husson, P., Jacquemin, J., Youngs, T.G.A., Kett, V.L., Hardacre, C., Costa Gomes, M.F.: Volumetric properties and enthalpies of solution of alcohols CkH2k+1OH (k = 1, 2, 6) in 1-methyl-3-alkylimidazolium bis(trifluoromethylsulfonyl)imide [C1CnIm][NTf2] n = 2, 4, 6, 8, 10 ionic liquids. J. Chem. Thermodyn. 43, 1708–1718 (2011)
Yasmeen, S., Riyazuddeen, Anwar, N.: Interaction of 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)-imide with methanol/dimethyl sulfoxide at (298.15, 303.15, 308.15, 313.15, 318.15, and 323.15) K: measurements and correlations of thermophysical properties. J. Mol. Liq. 221, 1207–1217 (2016)
Salinas, R., Pla-Franco, J., Lladosa, E., Montón, J.B.: Density, speed of sound, viscosity, and excess properties of binary mixtures formed by ethanol and bis(trifluorosulfonyl)imide-based Ionic liquids. J. Chem. Eng. Data 60, 525–540 (2015)
Andreatta, A.E., Arce, A., Rodil, E., Soto, A.: Physico-chemical properties of binary and ternary mixtures of ethyl acetate + ethanol + 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide at 298.15 K and atmospheric pressure. J. Solution Chem. 39, 371–383 (2010)
Wandschneider, A., Lehmann, J.K., Heintz, A.: Surface tension and density of pure ionic liquids and some binary mixtures with 1-propanol and 1-butanol. J. Chem. Eng. Data 53, 596–599 (2008)
Fatima, U., Riyazuddeen, Anwar, N., Montes-Campos, H., Varela, L.M.: Molecular dynamics simulation, molecular interactions and structural properties of 1-butyl-3-methylimidazolium bis(trifluoromethanesufonyl)imide + 1-butanol/1-propanol mixtures at (298.15–323.15 K) and 0.1 MPa. Fluid Phase Equib. 472, 9–21 (2018)
Lopes, J.N.C., Costa Gomes, M.F., Husson, P., Pádua, A.A.H., Rebelo, L.P.N., Sarraute, S., Tariq, M.: Polarity, viscosity, and ionic conductivity of liquid mixtures containing [C4C1im][Ntf2] and a molecular component. J. Phys. Chem. B 115, 6088–6099 (2011)
Ciocirlan, O., Croitoru, O., Iulian, O.: Densities and viscosities for binary mixtures of 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid with molecular solvents. J. Chem. Eng. Data 56, 1526–1534 (2011)
Ramos-Estrada, M., López-Cortés, I.Y., Iglesias-Silva, G.A., Pérez-Villaseñor, F.: Density, viscosity, and speed of sound of pure and binary mixtures of ionic liquids based on sulfonium and imidazolium cations and bis(trifluoromethylsulfonyl)imide anion with 1-propanol. J. Chem. Eng. Data 63, 4425–4444 (2018)
Vercher, E., Llopis, F.J., González-Alfaro, V., Miguel, P.J., Orchillés, V., Martínez-Andreu, A.: Volumetric properties, viscosities and refractive indices of binary liquid mixtures of tetrafluoroborate-based ionic liquids with methanol at several temperatures. J. Chem. Thermodyn. 90, 174–184 (2015)
González, E.J., Calvar, N., Fernández, P., Domínguez, A., Macedo, E.A.: Physical and excess properties for binary systems containing an alcohol and ionic liquid at T = 298.15 K. Procedia Eng. 42, 1383–1389 (2012)
Nickerson, S.D., Nofen, E.M., Chen, H., Ngan, M., Shindel, B., Yu, H., Dai, L.L.: A combined experimental and molecular dynamics study of iodide-based ionic liquid and water mixtures. J. Phys. Chem. B 119, 8764–8772 (2015)
Malham, I.B., Turmine, M.: Viscosities and refractive indices of binary mixtures of 1-butyl-3-methylimidazolium tetrafluoroborate and 1-butyl-2,3-dimethylimidazolium tetrafluoroborate with water at 298 K. J. Chem. Thermodyn. 40, 718–723 (2008)
Lu, X., Xie, H., Lei, Q., Fang, W.: Densities and viscosities of binary mixtures of 2,2-diethyl-1,1,3,3-tetramethylguanidinium bis(trifluoromethylsulfonyl)imide with methanol and ethanol. J. Chem. Thermodyn. 136, 44–53 (2019)
Chen, L., Chen, J., Song, Z., Cui, G., Xu, Y., Wang, X., Liu, J.: Densities, viscosities, and excess properties of binary mixtures of two imidazolide anion functionalized ionic liquids with water at T = (293.15 to 313.15) K. J. Chem. Thermodyn. 91, 292–300 (2015)
Rilo, E., Vila, J., Pico, J., García-Garabal, S., Segade, L., Varela, L.M., Cabeza, O.: Electrical conductivity and viscosity of aqueous binary mixtures of 1-alkyl-3-methyl imidazolium tetrafluoroborate at four temperatures. J. Chem. Eng. Data 55, 639–644 (2010)
Kamlet, M.J., Abboud, J.L., Taft, R.W.: The solvatochromic comparison method. 6. The π* scale of solvent polarities. J. Am. Chem. Soc. 99, 6027–6038 (1977)
Kamlet, M.J., Taft, R.W.: The solvatochromic comparison method. 1. The β-scale of solvent hydrogen-bond acceptor (HBA) basicities. J. Am. Chem. Soc. 98, 377–383 (1976)
Angell, C.A., Ansari, Y., Zhao, Z.: Ionic liquids: past, present, and future. Faraday Discuss. 154, 9–27 (2012)
Schreiner, C., Zugmann, S., Hartl, R., Gores, H.J.: Fractional Walden rule for ionic liquids: examples from recent measurements and a critique of the so-called KCl line for the Walden plot. J. Chem. Eng. Data 55, 1784–1788 (2010)
Huang, X., Margulis, C.J., Li, Y., Berne, B.J.: Why is the partial molar volume of CO2 so small when dissolved in a room temperature ionic liquid? Structure and dynamics of CO2 dissolved in [Bmim+][PF6−]. J. Am. Chem. Soc. 127, 17842–17851 (2005)
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YY: conceptualization, supervision, writing-original draft preparation; SH: investigation; KK: investigation; TM: investigation; KK: investigation; TT: formal analysis, visualization; AS: writing- reviewing and editing.
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Yoshimura, Y., Hattori, S., Kitawaki, K. et al. Changes in the Thermodynamic Properties of the Ionic Liquid 1-Butyl-3-methylimidazolium Bis(trifluoromethanesulfonyl)amide Upon Addition of Primary Alcohols. J Solution Chem 50, 995–1007 (2021). https://doi.org/10.1007/s10953-021-01098-z
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DOI: https://doi.org/10.1007/s10953-021-01098-z